TW201200569A - Water-based ink composition for ballpoint pens - Google Patents

Abstract

The present invention provides a novel ink composition for ballpoint pens, which combines the advantages of water-based ink for ballpoint pens and oil-based ink for ballpoint pens. This invention relates to a water-based ink composition for ballpoint pens, wherein, for an aqueous phase comprising a pigment dispersant, an oily phase comprising an oily solution obtained by dissolving a dye in an organic solvent is contained as an oil-in-water emulsion.

Description

201200569 六、發明說明： c發明戶斤屬之技術領域3 發明領域 本發明係有關於水性圓珠筆用墨水組成物，具體而 言，係有關於一種水性相（aqueous phase)由顏料分散體所構 成且對於前述水性相係以水中油型乳液狀態含有業已溶解 於油性相之染料的水性圓珠筆用墨水組成物。 C 才支 4标 發明背景 水性圓珠筆之特徵可舉出低黏度且墨水流出量多，書 寫時流到輕盈，並可得到鮮明的描線，但相反地，卻有著 書寫時有斷水感到的缺點。還有，其係使用顏料或染料作 為著色材，而顏料雖有而ί候性高的優點，但著色力弱，不 易得到高描線濃度。又，若為了提高濃度而多量添加顏料， 則會產生致使分散穩定性受損的問題。再者，其調色的多 樣化也不及染料。另一方面，染料具有著色力與調色自由 度高的優點，但耐候性低，而且一旦有水附著時，描線就 容易擴散暈開。 油性圓珠筆因墨水黏度高，墨水流出量少，故書寫時 沒有斷水感，描線鮮少產生染潰為其優點，然而在書寫時 多感遲滯。又，可作為著色材使用的染料因具有對水不溶 或難溶的分子結構，故具備耐水性，使用水溶性染料之墨 水常見的對水擴散暈開並不會發生。 近年，亦開發使油性墨水之黏度降低、使書寫質感提201200569 VI. INSTRUCTIONS: C TECHNICAL FIELD OF THE INVENTION The present invention relates to an ink composition for a water-based ballpoint pen, and more particularly to an aqueous phase composed of a pigment dispersion and The water-based ball-point pen ink composition containing the dye which has been dissolved in the oil phase in the aqueous oil-based emulsion state is contained in the aqueous phase. C. The standard of the invention is that the water-based ballpoint pen is characterized by low viscosity and a large amount of ink flowing out, which is light in writing, and can obtain a sharp line, but conversely, it has the disadvantage of being broken when writing. Further, although a pigment or a dye is used as a coloring material, the pigment has the advantage of high urethane, but the coloring power is weak, and a high line concentration is not easily obtained. Further, if a large amount of the pigment is added in order to increase the concentration, there is a problem that the dispersion stability is impaired. Furthermore, the coloring is not as diverse as the dye. On the other hand, the dye has the advantages of a coloring power and a high degree of freedom in color grading, but the weather resistance is low, and when water adheres, the line is easily diffused and smudged. Because of the high viscosity of the ink and the low outflow of the ink, the oily ballpoint pen has no water-breaking feeling when writing, and the drawing line has little advantage of dyeing and squeezing. However, it is often delayed in writing. Further, since the dye which can be used as a coloring material has a molecular structure which is insoluble or poorly soluble in water, it has water resistance, and the water which is often used for water diffusion using a water-soluble dye does not occur. In recent years, it has also developed to reduce the viscosity of oil-based inks and improve the writing quality.

Iff 3 2〇12〇〇569 =的油性圓珠筆。但是，低黏度的油性墨水由於書寫流出 ’故描線乾燥性惡化，而成為墨水朝紙張背面透印、 漏水的原因。 曰本特開2004-11561號公報中，記載了 一種低黏度的 '由丨生圓珠筆墨水’係採用業已於有機溶劑中含水的油中水 〇)型有機溶劑。但是，該墨水在保存穩定性上有問題， 、由於墨水組成的大半是有機溶劑，故一旦使書寫流出量 増加，便會產生透印。 日本特開2007-327003號公報中，記載了一種油中水 〇V/〇)型乳液墨水組成物，係預先使顏料含在水性成分中， 再將之與油性成分混合，藉此使顏料業已分散的水性成分 所構成的水滴可分散於油性成分中。藉由使用該墨水組成 物’而揭示了使書寫感等有所改善的圓珠筆墨水，然而， 在長期保存時，水滴會合一而變成局部存在化，諸如此類 等欠缺穩定性。又，由於墨水組成物中的油性成分量偏多， 故一旦如水性圓珠筆般使書寫流出量增加，則在透印、描 線乾燥性惡化上極為顯著。 又，在曰本特開昭55-152768號公報中，記載了 一種可 以橡皮擦消抹之書寫用墨水，係使顏料分散於以聚合物、 溶解前述聚合物之溶劑所構成的聚合物溶液中而得到業已 著色之組成物，且將該组成物於水中乳化分散而成者。但 疋，该墨水之著色材為顏料，分散粒子屬於非常高黏度， 故若使用於圓珠筆，則書寫性差，而且分散粒子容易合一 而〉儿降，在保存穩定性上也有問題。 4 201200569 曰本特開2004-323618號公報中，記載了 一種書寫用具 用多色墨水，係於書寫時，使含有水溶性染料之水溶性墨 水與含有油溶性染料之油溶性墨水所構成的墨水組成物振 動，以形成不穩定的乳液，其書寫線短且呈不規則的連續 性變化。其中所載之意係該墨水在靜置狀態下會分離為2 層，並不適合用作一般的圓珠筆墨水。 本發明人所設計之日本專利申請之特願2008-145150 號說明書中，揭示了一種兼具水性圓珠筆與油性圓珠筆之 優點、且墨水性狀為水中油型乳液之水性圓珠筆用墨水組 成物。利用水性相，而可實現高流出量且輕盈流利的書寫 感，並利用油性相之油膜，而可提供描線無染潰或透印、 書寫時沒有斷水感之物。特願2008-145150號說明書中所記 載之發明實乃空前之水性圓珠筆用墨水組成物，具有優異 的性能’然而另一方面，該乳液因高黏性’且所使用的溶 劑基於穩定性而以高沸點為佳，因此，該乳液本身揮發性 偏低。在該墨水中’一旦乳液濃度高，就有描線乾燥性惡 化的問題，又’在濃度低時，則有描線濃度不充分的問題。 其他問題方面’作為著色材之染料液主體之乳液有著耐光 性不易克服的問題。特願2008-145150號說明書之實施例2 中’記載了添加碳黑的摻混配方，然而仍不足以解決前述 諸多問題’因而冀望更進一步的改良。 先行技術文獻 【專利文獻】 專利文獻1曰本特開2004-115611號公報 201200569 專利文獻2日本特開2007-327003號公報 專利文獻3日本特開昭55-152768號公報 專利文獻4日本特開2004-323618號公報 專利文獻5日本特願2008-145150號說明書。 【發明内容】 發明概要 發明欲解決之課題 如上所述，水性圓珠筆、油性圓珠筆係各自具有優點 與缺點。本發明之目的就在於提供一種兼具兩者優點之新 穎水性圓珠筆用墨水組成物。 用以欲解決課題之手段 本發明人經專精致力之研究，結果發現，在由顏料分 散體所構成之水性相中，將油性染料溶液以水中油型乳液 加以組合，藉此即可解決前述課題，而完成了本發明。 亦即，本發明係： (1) 一種水性圓珠筆用墨水組成物，係對於顏料分散體 所構成之水性相，以水中油型乳液之狀態含有油性相，且 該油性相含有業已使染料溶解於有機溶劑中之油性溶液。 (2) 如（1)所記載之水性圓珠筆用墨水組成物，其中前 述油性溶液之全溶劑中，分子骨架中具有一個以上芳香環 的溶劑係以質量基準計佔50%以上，且前述墨水組成物含 有分子骨架中具有一個以上芳香環的乳化劑。 (3) 如（2)所記載之水性圓珠筆用墨水組成物，其中前 述乳化劑至少含有乙烯氧化物加成莫耳數為40以上的芳香 6 201200569 族系乳化劑。 (4) 如（1)〜(3)中任一項所記載之水性圓珠筆用墨水組 成物，其中前述油性溶液之溶劑的沸點在200°C以上。 (5) 如（1)〜(4)中任一項所記載之水性圓珠筆用墨水組 成物，其於25°C下對水的溶解度以質量基準計係1%以下， 且分子骨架中具有一個以上芳香環的溶劑在前述油性溶液 之全溶劑中以質量基準計係佔5 0%以上。 (6) 如（1)〜(5)中任一項所記載之水性圓珠筆用墨水組 成物，其中前述水中油型乳液之油滴的平均粒徑為200nm 以下。 (7) 如（1)〜(6)中任一項所記載之水性圓珠筆用墨水組 成物，其中該墨水組成物中所佔的油性相成分之比例以質 量基準計係1〜20%。 (8) 如（1)〜(7)中任一項所記載之水性圓珠筆用墨水組 成物，其中前述顏料分散體中所含的分散劑為苯乙烯丙烯 酸樹脂。 發明效果 本發明之水性圓珠筆用墨水組成物之特徵在於：其係 於水性相中含顏料分散體，且係以水中油型乳液之狀態含 有染料液。藉此，不僅具備習知顏料類型之水性圓珠筆輕 盈流利書寫感的優點、及顏料所持有的对水•对候性，再 加上水中油型乳液可發揮以下作用效果，亦即，利用油性 相之油膜，可提供無斷水感的書寫感，進一步藉由採用染 料，而可達成色濃度提升與自由度高的調色變化，同時可Iff 3 2〇12〇〇569 = oily ballpoint pen. However, since the low-viscosity oil-based ink is written out, the drying property of the ink is deteriorated, and the ink is printed on the back side of the paper and leaks. Japanese Laid-Open Patent Publication No. 2004-11561 discloses a low-viscosity 'yellow ballpoint pen ink' which is an organic solvent which is water-containing in an organic solvent. However, this ink has a problem in storage stability, and since most of the ink composition is an organic solvent, once the writing outflow amount is increased, offset is generated. JP-A-2007-327003 discloses an oil-in-water V/〇-type emulsion ink composition in which a pigment is contained in an aqueous component and then mixed with an oil component, whereby the pigment is already The water droplets composed of the dispersed aqueous components can be dispersed in the oily component. By using the ink composition', a ballpoint pen ink which improves the writing feeling and the like is revealed. However, in the long-term storage, the water droplets may merge to become localized, and the like, etc., lack stability. Further, since the amount of the oily component in the ink composition is excessively large, the amount of writing and outflow is increased as in the case of a water-based ballpoint pen, which is remarkable in the deterioration of the offset and the drying property. Further, Japanese Laid-Open Patent Publication No. Sho 55-152768 discloses a writing ink which can be erased by an eraser, and which disperses a pigment in a polymer solution composed of a polymer and a solvent in which the polymer is dissolved. The composition which has been colored is obtained, and the composition is emulsified and dispersed in water. However, the color of the ink is a pigment, and the dispersed particles are very high in viscosity. Therefore, if used in a ballpoint pen, the writing property is poor, and the dispersed particles are easily combined, and there is a problem in storage stability. Japanese Laid-Open Patent Publication No. 2004-323618 discloses a multi-color ink for writing instruments, which is an ink composed of a water-soluble ink containing a water-soluble dye and an oil-soluble ink containing an oil-soluble dye during writing. The composition vibrates to form an unstable emulsion with a short writing line and an irregular continuity change. It is intended to separate the ink into two layers when it is still in use, and is not suitable for use as a general ballpoint pen ink. In the specification of Japanese Patent Application No. 2008-145150, which is incorporated by the present inventors, the ink composition for a water-based ballpoint pen having the advantages of a water-based ballpoint pen and an oil-based ballpoint pen and having an ink property of an oil-in-water emulsion is disclosed. By using the aqueous phase, it is possible to achieve a high outflow and a light and fluent writing feeling, and to use an oil film of an oily phase, and it is possible to provide a product which has no dyeing or offset, and which has no water-breaking feeling when written. The invention described in the specification of the Japanese Patent Application No. 2008-145150 is an unprecedented ink composition for a water-based ballpoint pen, and has excellent performance. However, on the other hand, the emulsion is highly viscous and the solvent used is based on stability. The high boiling point is preferred, so the emulsion itself is less volatile. In the ink, when the concentration of the emulsion is high, there is a problem that the drying property of the line is deteriorated, and when the concentration is low, there is a problem that the concentration of the line is insufficient. In other problems, the emulsion of the main body of the dye liquid as a coloring material has a problem that light resistance is not easily overcome. In the second embodiment of the specification of the Japanese Patent Application No. 2008-145150, the blending formula of the addition of carbon black is described, but it is still insufficient to solve the aforementioned problems, and further improvement is expected. For example, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2008-145150. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION As described above, each of the water-based ballpoint pen and the oil-based ballpoint pen has advantages and disadvantages. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel ink composition for a water-based ballpoint pen which has both advantages. Means for Solving the Problem The inventors of the present invention have found out that the oily dye solution is combined with an oil-in-water emulsion in an aqueous phase composed of a pigment dispersion, thereby solving the foregoing. The subject matter has been completed. That is, the present invention is: (1) An aqueous ink composition for a ballpoint pen, which comprises an oily phase in the form of an oily emulsion in the form of an aqueous phase composed of a pigment dispersion, and the oily phase contains a dye which has been dissolved in the oily phase. An oily solution in an organic solvent. (2) The ink composition for a water-based ballpoint pen according to (1), wherein a solvent having one or more aromatic rings in the molecular skeleton accounts for 50% or more by mass based on the total mass of the oil solution, and the ink composition is The substance contains an emulsifier having more than one aromatic ring in the molecular skeleton. (3) The ink composition for a water-based ballpoint pen according to the above aspect, wherein the emulsifier comprises at least an aromatic emulsifier having an ethylene oxide addition number of 40 or more and a urethane 6 201200569 emulsifier. The ink composition for a water-based ballpoint pen according to any one of the above-mentioned, wherein the solvent of the oily solution has a boiling point of 200 ° C or higher. (5) The ink composition for a water-based ballpoint pen according to any one of (1) to (4), wherein the solubility in water at 25 ° C is 1% or less by mass, and one of the molecular skeletons The solvent of the above aromatic ring accounts for more than 50% by mass based on the total solvent of the above oily solution. (6) The ink composition for a water-based ballpoint pen according to any one of (1) to (5) wherein the oil droplets of the oil-in-water emulsion have an average particle diameter of 200 nm or less. (7) The ink composition for a water-based ballpoint pen according to any one of (1) to (6), wherein the ratio of the oily phase component in the ink composition is 1 to 20% by mass. The ink composition for a water-based ballpoint pen according to any one of the above-mentioned, wherein the dispersing agent contained in the pigment dispersion is a styrene acryl resin. EFFECTS OF THE INVENTION The ink composition for a water-based ballpoint pen of the present invention is characterized in that it contains a pigment dispersion in an aqueous phase and contains a dye liquid in the state of an oil-in-water emulsion. In this way, not only the advantages of the light and fluent writing feeling of the water-based ballpoint pen of the conventional pigment type, but also the water-pairing property held by the pigment, and the oil-based emulsion in water can exert the following effects, that is, the oily property is utilized. The oil film of the phase can provide a sense of writing without water loss, and further, by using a dye, a color change with a high color density and a high degree of freedom can be achieved.

S 7 201200569 提供耐水性。本發明係提供一種兼具水性圓珠筆墨水與油 性圓珠筆墨水之優點，甚且保存穩定性佳的水性圓珠筆墨 水組成物。 【實施方式3 用以實施發明之形態 本發明之.墨水組成物，具有下述構成：水性相由顏料 分散體所構成，且油性染料溶液係以水中油型乳液之狀態 含在前述水性相中。以下，古羊鈿勺B日士义 。手細δ兄明本發明之墨水組成物 的成分。 〜叫丨土祁，保於有機溶劑中業已 使至少作為著色材之染料溶_油性溶液所構成。作為由 性溶液的溶劑方面，分子骨架中具有芳香環的溶劑因溶解 染料這一點而屬適宜’只要是具有芳香環的溶劑，則任何 溶劑皆可制。較適當者係分子«巾具衫香環的溶劑 相對於油性相溶液全溶劑，以f量基準計在观 佳，70%以上最佳。 两 尤其，若考量到不僅可溶解染料，並且再加上不 相溶、所形成之乳液的保存穩定性佳、及安全 ” 更為適當的溶劑係分子内具有—個以上的料環问且容添 對水的溶解度在饥時為lg/⑽㈣下之物。若/ woog，則所得之乳液會變得不穩定而可能會歷時 相分離。在油性溶液中’分子内具有—個 溶劑對水之溶解度在坑時為下之溶劑， 溶劑之質量基準計在50%以上為佳，70〇/〇以上最佳。’、王 201200569 又，可用於本發明之油性溶液的溶劑係以相對上屬低 揮發性之溶劑為宜。 溶劑係可由選自以下所示溶劑之例子中的1種溶劑所 構成、或亦可由多數種溶劑所構成。 可用於本發明之油性溶液的溶劑之例子，可舉苄醇、 乙二醇一苯醚'乙二醇一苄基醚、丙二醇一苯醚、二乙二 醇一苯醚、烷基磺酸苯酯、苯二甲酸丁酯、苯二甲酸乙基 己酯、苯二曱酸十三酯'苯偏三酸乙基己酯、二乙二醇二 苯甲酸酯、二丙二醇二苯曱酸酯、二甲苯、曱苯等。該等 之中，尤其在25°C時對水的溶解性為lg/l〇〇g以下之乙二醇 一苄基醚、丙二醇一苯醚、烷基磺酸苯酯、苯二甲酸乙基 己酯、苯二甲酸十三酯、苯偏三酸乙基己酯、二乙二醇二 苯甲酸酯、二丙二醇二苯甲酸酯、液狀二甲苯樹脂、曱苯、 二甲苯等可舉作為適當溶劑。該等之中，最佳者係在25°C 時對水的溶解性為0.1g/100g以下之烷基磺酸苯酯、苯偏三 酸乙基己酯、二乙二醇二苯曱酸酯、二丙二醇二苯曱酸酯 等及其他如液狀二甲苯樹脂、甲苯、二曱苯等可舉作為適 當溶劑。 又，基於使染料溶解之作業上安全性之觀點，還有抑 制高溫時因乳液内壓上升所造成的不穩定化之觀點，而以 沸點為200°C以上之溶劑為佳。適當的溶劑之例，可舉苄 醇、乙二醇一苯醚、乙二醇一苄基醚、丙二醇一苯醚、二 乙二醇一苯醚、烷基磺酸苯酯、苯二甲酸丁酯、苯二曱酸 乙基己酯、苯二甲酸十三酯、苯偏三酸乙基己酯、二乙二 9 201200569 醇二苯曱酸酯、二丙二醇二苯甲酸酯等。 又，本發明之油性溶液中，除了上述具有芳香環的溶 劑之外，可含有任意的輔助溶劑。例如，可使用選自醇類、 多元醇類、二元醇醚類、烴類、酯類之溶劑等，但是與水 無限相溶的溶劑因會朝水性相擴散、引起油滴合一，故不 應大量使用。以油性溶液中的全溶劑之質量％計在1 〇%以内 為宜。 作為醇類者，以碳原子數2以上的脂肪族醇為佳，可舉 例如乙醇、正丙醇、異丙醇、正丁醇、異丁醇、三級丁基 醇、1-戊醇、異戊基醇、二級戊基醇、3-戊醇、三級-戊基 醇、正己醇、甲基戊基醇、2-乙基丁醇、正庚醇、2-庚醇、 3-庚醇、正辛醇、2-辛醇、2-乙基己醇、3,5,5-三曱基己醇、 壬醇、正癸醇、十一醇、正癸醇、三甲基壬基醇、三癸醇、 十七醇、環己醇、2-曱基環己醇或其他各式各樣的高級醇等。 又，作為多元醇類者，以分子内有2個以上的碳原子、 2個以上的羥基之多元醇為佳，可舉例如乙二醇、二乙二 醇、3-甲基-1,3 丁二醇、三乙二醇、二丙二醇、1,3丙二醇、 1，3丁二醇、1,5戊二醇、己二醇、辛二醇等。 作為二元醇醚類者，可舉例如甲基異丙基醚、乙基醚、 乙基丙基醚、乙基丁基醚、異丙基醚、丁基醚、己基醚、 2-乙基己基醚、乙二醇一己基醚、乙二醇一-2-乙基丁基醚、 乙二醇一甲基醚、乙二醇一乙基醚、乙二醇一丁基醚、二 乙二醇一曱基醚、二乙二醇一乙基醚、二乙二醇一丁基醚、 三乙二醇一丁基醚、四乙二醇一丁基醚、3-曱基-3-甲氧基 10 201200569 丁醇、3-曱氧基-1-丁醇、丙二醇一甲基醚、丙二醇一乙 基醚、丙二醇一丙基醚、丙二醇—丁基醚、丙二醇三級丁 基醚二丙二醇一曱基醚、二丙二醇一乙基醚 '二丙二醇一 丙基醚、二丙二醇一丁基醚、三丙二醇一曱基醚、三丙二 醇—丁基醚、四丙二醇一丁基醚等。 作為烴類者，可舉己烷、異己烷、庚烷、辛烷、壬烷、 癸烷等直鏈烴類或環己烷、曱基環己烷、乙基環己烷等環 狀烴類。 作為酯類的輔助溶劑者，可舉例如丙二醇曱基醚乙酸 酯、丙二醇二乙酸酯、3_曱基_3_曱氧基丁基乙酸酯、丙二 醇乙基醚乙酸酯、乙二醇乙基醚乙酸酯、蟻酸丁酯、蟻酸 異丁酯、蟻酸異戊酯 '醋酸丙酯、醋酸丁酯、醋酸異丙酯、 醋酸異丁酯、醋酸異戊酯、丙酸曱酯 '丙酸乙酯、丙酸丙 酯、丙酸異丁酯、丙酸異戊酯、丁酸甲酯、丁酸乙酯、丁 酸丙酯、異丁酸甲酯、異丁酸乙酯、異丁酸丙酯、戊酸曱 酯、戊酸乙酯、戊酸丙酯、異戊酸曱酯、異戊酸乙酯、異 戊酸丙酯、三甲基醋酸甲酯、三甲基醋酸乙酯、三曱基醋 酸丙酯、己酸甲酯、己酸乙酯、己酸丙酯、辛酸甲酯、辛 酸乙酯、辛酸丙酯、月桂酸曱酯、月桂酸乙酯、油酸甲酯、 油酸乙酯、辛酸三甘油酯、檸檬酸三丁基乙酸酯' 氧基硬 脂酸辛酯、丙二醇一蓖麻油酸酯、2-羥基異丁酸曱酯、3-甲氧基丁基乙酸酯等各種酯。 又’分子内不具有羥基的輔助溶劑方面，可使用二醚 或二酯’具體而言’可舉例如乙二醇二乙基醚、乙二醇二 11 201200569 丁基趟、一乙二醇二乙基醚、二乙二醇二丁烏鍵 醇二甲基醚、二丙二醇二甲基醚等。 本發明之墨水組成物之油性相中的著色材係染； 使用的染料只要是溶解於上述溶劑之物，—如 所 又/由性墨水矣且 成物中所使用的任何染料皆可使用β作為有關本發明之油 溶性染料者，可使用通常用於染料墨水組成物中的直接染 料、酸性染料、鹼性染料、媒染•酸性媒染染料、醇溶型 染料、偶氮染料、硫化•硫化甕染料、甕染料、分散染料、 油溶性染料、食用著色料、金屬錯合物染料、造鹽染料、 業已將染料染色於樹脂之染料等之中任意者。该等之中’ 易於溶解於有機溶劑之造鹽染料等之醇溶型染科、.油溶性 染料等，在溶解性、乳液穩定性之方面來看較為適宜。尤 其適宜之染料為油溶性染料。 染料之下限摻混量，係以墨水組成物全量么質量基準 計0_3%以上為佳。若不足〇 3%，則著色力不充分。又，上 限之摻混量係以油性溶液總量之質量基準計70%以下為 佳。若超過70%，則染料的溶解變得困難，作為圓珠筆之 墨水組成物而言並不適宜。尤其適宜者係以墨水組成物之 質量基準計在1〜3%的範圍，且以油性溶液之質聋基準計在 10〜60%的範圍。 作為油性墨水組成物中所使用的造鹽染科方面’有 VALIFASTCOLAR (凡里飛速特彩色)(註冊商楳，東方化學 工業（股）(Orient Chemical Industries，Ltd.)數）八· Spilon(愛染絲匹絡）染料、Aizen Spilon SOT染科(1主冊商標 12 201200569 名，保土谷化學工業(股)製）。 用於將染料染色於樹脂之染料，有keiko-Colot(凱克科 羅特)MPI-500系列、keiko-Colot MPI-500C系列、keiko-Colot NKS-1000系列（註冊商標，日本螢光化學（股）製）。 油性相中的著色材，只要是可維持乳液之穩定性，可 使用少量的顏料與染料組合。使用顏料的情況下，顏料的 量係以油性溶液之質量基準計在1 〇%以下為佳。若超過 10%，則在乳液穩定性上會有所不妥。 在油性相中，可與染料組合使用的顏料，可舉碳黑、 氧化鈦等無機顏料、酞青素系顏料、偶氮系顏料、吡咯並 吡咯二酮(Diketopyrrolopyrrole)系顏料、蒽醌系顏料、茈系 顏料、1-異吲哚啉酮系顏料、煃吖啶酮系顏料等各種有機 顏料。 用以周製本發明之墨水組成物的油性溶液中，可使用 樹脂以調整黏度。前述油性溶液的黏度，在不含乳化劑的 狀態下，於25 °C 、剪斷速度3.83/秒時宜為 500〜1,000,00〇111?3.3。黏度若不足5〇〇111?3.8，則書寫時 會產生斷水感，作為水中油型所獲致之油性墨水方面的性 能不易發揮。甚且’乳液的穩定性上也不佳。若超過 l，000,000mPa · s ’則筆感會變凝重，作為圓珠筆之墨水組 成物不適宜。於25 °C 、剪斷速度3.83/秒時為 3,000〜500,000mPa · s的黏度範圍特別適宜。 本發明之墨水組成物中可使用的樹脂之具體性例子， 可舉出酮樹脂、續醯胺樹脂、馬來酸樹脂、祐烯樹脂、萜 13 201200569 烯酴樹脂（terpene phen〇1奶比）、酯膠、二曱苯樹脂、醇酸 樹脂、盼樹脂、松脂、聚乙烯基吡咯啶酮、聚乙烯基丁醛 樹脂、聚乙烯基醇、丙烯酸系樹脂、三聚氰胺系樹脂、纖 維素系樹脂等之天然及合成樹脂，可使用該等之丨種或2種 以上。 前述油性溶液中的染料及其他添加物的量，係以作為 固形物成分漢度為全油性溶液之質量基準計3〜70%為佳。 固形物成分濃度若小於3%，則變得無法賦予充分的黏性。 若超過70°/。’則染料的溶解變得困難，以圓珠筆的墨水組 成物而言並不適宜。固形物成分濃度以在1〇%〜60%之範圍 特佳。 本發明之墨水組成物之水性相係由顏料分散體所構 成。例如’該顏料分散體係採用離子交換水、精製水之顏 料分散體。作為顏料者係可使用碳黑、氧化鈦等之無機顏 料、酞青素系顏料、偶氮系顏料、吡咯並吡咯二酮系顏料、 蒽醌系顏料、茈系顏料、1-異吲哚啉酮系顏料、煃吖啶酮 系顏料等之各種有機顏料。 例如’可舉出 C.I.Pigment Black (C.I·顏料黑）1，7 ' C.I.Pigment Yellow (C.I.顏料黃）1，2, 3, 12, 13, 14, 16, 17, 20, 24, 34, 35, 42, 53, 55, 65, 73, 74, 75, 81，83, 86, 93, 94, 95, 97, 98, 99, 100, 101，104, 108, 109, 110, 114, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151，153, 154, 155，166，167，168, 173C, 174，180, 185 等；C.I. Pigment Red (C.I.顏料紅）1，2, 3, 5, 7, 8, 9, 10, 12, 16, 17, 19, 22, 38, 41， 14 201200569 43, 48, 48 : 2, 48 : 3, 49, 50 : 1，52, 53, 53 : 1，57, 57 : 1，58 : 2, 60, 63 : 1，63 : 2,64 : 1，86, 88, 90, 9, 112, 122, 123, 127, 146, 149, 166, 168, 170, 175, 176, 177, 179, 180, 181, 184, 185, 189, 190, 192, 194, 198, 202, 206, 207, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 245, 254, 225 等；C.I. Pigment Blue (C_I·顏料藍）1，2, 3，15 : 1, 15 : 2，15 : 3, 15 : 4, 15 : 6, 16, 17, 22, 25, 60, 64, 66 等；C.I. Pigment Orannge (C_I.顏料橙）5, 10, 13, 16, 36, 40, 43, 48, 49, 51，55, 59, 61, 71 等；C.I. Pigment Violet(C.I.顏料紫）1, 3, 5 : 1, 16, 19, 23, 29, 30, 31, 33, 36, 37, 38, 40, 42, 50等；C.I. Pigment Green (C.I.顏料綠）7，10，36等；C.I· Pigment Brown(C.I.顏料 棕)23, 25, 26等。 分散於水性相之顏料的顏色、與溶解於油性相之染料 的顏色可相同亦可相異。在使用與顏料之顏色屬相同顏色 之染料時，可藉由染料使墨水的色彩變得鮮明，同時可提 升色濃度。在使用與顏料之顏色屬不同顏色之染料時，可 得到自由度高的調色變化。 用以得到顏料分散體的分散劑，可使用各種市售之 物’並無特別限定，而從與並存之水中油型乳液的相性、 保存穩定性之方面來看，以高分子樹脂系分散劑為佳，且 敢好與作為乳化劑用以形成乳液的材料不同。例如，可使 用笨乙烯丙烯酸樹脂（styrene acrylic resin)或聚氧乙稀系分 政劑。尤其適宜的分散劑是屬高分子聚合物的苯乙烯丙稀 酸樹脂。S 7 201200569 provides water resistance. The present invention provides a water-based ballpoint ink composition which combines the advantages of a water-based ballpoint pen ink and an oil-based ballpoint pen ink, and which has excellent storage stability. [Embodiment 3] The ink composition of the present invention has the following structure: the aqueous phase is composed of a pigment dispersion, and the oily dye solution is contained in the aqueous phase in the state of an oil-in-water emulsion. . Below, the ancient sheep 钿 spoon B 日士义. The hand is a component of the ink composition of the present invention. ~ 丨 丨 祁 祁 祁 祁 祁 祁 祁 祁 保 保 保 保 保 保 保 保 保 保 保 有机 有机 有机 有机 有机 有机 有机As the solvent of the solvent, the solvent having an aromatic ring in the molecular skeleton is suitable for dissolving the dye. Any solvent can be used as long as it is a solvent having an aromatic ring. The solvent of the appropriate molecule is the solvent of the aroma of the towel. Compared with the total solvent of the oily phase solution, it is better than the amount of f, and 70% or more is the best. In particular, if it is considered that not only the dye can be dissolved, but also the immiscible, the emulsion formed is excellent in storage stability and safer. More suitable solvent molecules have more than one material in the molecule. The solubility of water in water is lg/(10)(4) when hunger. If / woog, the resulting emulsion will become unstable and may phase separate. In oily solution, there is a solvent in the molecule. Solubility is the solvent under the pit, and the mass of the solvent is preferably 50% or more, preferably 70 〇/〇 or more. ', Wang 201200569 Further, the solvent which can be used in the oily solution of the present invention is relatively low in relative The solvent is preferably a solvent selected from the group consisting of the solvents shown below, or may be composed of a plurality of solvents. Examples of the solvent which can be used in the oily solution of the present invention include benzylic acid. Alcohol, ethylene glycol monophenyl ether 'ethylene glycol monobenzyl ether, propylene glycol monophenyl ether, diethylene glycol monophenyl ether, phenyl alkyl sulfonate, butyl phthalate, ethyl hexyl phthalate , decyl phthalate, trimellitic acid Hexyl hexyl ester, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, xylene, toluene, etc. Among these, especially in 25 ° C, the solubility in water is lg / l 〇 Glycol monobenzyl ether, propylene glycol monophenyl ether, phenyl sulfonate, ethyl hexyl phthalate, tridecyl phthalate, ethylhexyl trimellitate, diethyl Glycol dibenzoate, dipropylene glycol dibenzoate, liquid xylene resin, toluene, xylene, etc. may be mentioned as suitable solvents. Among these, the best one is water at 25 ° C. The solubility is 0.1 g/100 g or less of phenyl sulfonate, ethyl hexyl trimellitate, diethylene glycol diphenyl phthalate, dipropylene glycol dibenzoate, etc. and others such as liquid Toluene resin, toluene, diphenylbenzene, and the like can be used as a suitable solvent. From the viewpoint of safety in the operation of dissolving the dye, it is also possible to suppress the instability caused by the increase in the internal pressure of the emulsion at a high temperature. A solvent having a boiling point of 200 ° C or higher is preferred. Examples of suitable solvents include benzyl alcohol, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and C. Alcohol monophenyl ether, diethylene glycol monophenyl ether, phenyl sulfonate, butyl phthalate, ethylhexyl phthalate, tridecyl phthalate, ethylhexyl trimellitate Further, the oily solution of the present invention may contain any auxiliary solvent in addition to the solvent having an aromatic ring, for example, in the case of the oily solution of the present invention. A solvent selected from the group consisting of alcohols, polyhydric alcohols, glycol ethers, hydrocarbons, and esters can be used, but a solvent which is infinitely compatible with water may diffuse toward the aqueous phase and cause oil to be detached, so it should not be used. It is preferably used in an amount of not less than 1% by mass based on the total mass of the solvent in the oily solution. The alcohol is preferably an aliphatic alcohol having 2 or more carbon atoms, and examples thereof include ethanol, n-propanol, and the like. Propanol, n-butanol, isobutanol, tert-butyl alcohol, 1-pentanol, isoamyl alcohol, secondary amyl alcohol, 3-pentanol, tertiary amyl alcohol, n-hexanol, methyl Amyl alcohol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 2-ethylhexanol, 3,5,5-trimethyl already , sterol, n-nonanol, undecyl alcohol, n-nonanol, trimethylnonyl alcohol, triterpene alcohol, heptadecyl alcohol, cyclohexanol, 2-nonylcyclohexanol or other various advanced Alcohol, etc. Further, as the polyol, a polyol having two or more carbon atoms and two or more hydroxyl groups in the molecule is preferable, and examples thereof include ethylene glycol, diethylene glycol, and 3-methyl-1,3. Butylene glycol, triethylene glycol, dipropylene glycol, 1,3 propanediol, 1,3 butanediol, 1,5 pentanediol, hexanediol, octanediol, and the like. Examples of the glycol ethers include methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl ether, butyl ether, hexyl ether, and 2-ethyl group. Hexyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Alcohol monodecyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, 3-mercapto-3-yl Oxygen 10 201200569 Butanol, 3-decyloxy-1-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol-butyl ether, propylene glycol tert-butyl ether dipropylene glycol Monodecyl ether, dipropylene glycol monoethyl ether 'dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monodecyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, and the like. Examples of the hydrocarbons include linear hydrocarbons such as hexane, isohexane, heptane, octane, decane, and decane, and cyclic hydrocarbons such as cyclohexane, nonylcyclohexane, and ethylcyclohexane. . Examples of the auxiliary solvent of the ester include propylene glycol decyl ether acetate, propylene glycol diacetate, 3-mercapto-3-indolyl butyl acetate, propylene glycol ethyl ether acetate, and B. Glycol ethyl ether acetate, butyl formic acid, isobutyl formic acid, isoamyl formate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate, decyl propionate 'ethyl propionate, propyl propionate, isobutyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate, Propyl isobutyrate, decyl valerate, ethyl valerate, propyl valerate, decyl isovalerate, ethyl isovalerate, propyl isovalerate, methyl trimethylacetate, trimethylacetic acid Ethyl ester, trimethyl propyl acetate, methyl hexanoate, ethyl hexanoate, propyl hexanoate, methyl octanoate, ethyl octanoate, propyl octanoate, decyl laurate, ethyl laurate, oleic acid Ester, ethyl oleate, triglyceride octanoate, tributyl acetate octyl octyl oxystearate, propylene glycol ricinoleate, decyl 2-hydroxyisobutyrate, 3-methoxybutyl Base B Esters, and other esters. Further, in terms of an auxiliary solvent having no hydroxyl group in the molecule, a diether or a diester may be used. Specifically, for example, ethylene glycol diethyl ether, ethylene glycol II 11 201200569 butyl hydrazine, monoethylene glycol II may be used. Ethyl ether, diethylene glycol dibutylol dimethyl ether, dipropylene glycol dimethyl ether, and the like. The coloring material in the oily phase of the ink composition of the present invention is dyed; the dye used may be any one of the dyes used in the above-mentioned solvent, such as the ink/ink ink, and any dye used in the product. As the oil-soluble dye of the present invention, a direct dye, an acid dye, a basic dye, a mordant, an acid mordant dye, an alcohol-soluble dye, an azo dye, a vulcanized sulfonium sulfide which are generally used in a dye ink composition can be used. A dye, an anthraquinone dye, a disperse dye, an oil-soluble dye, a food coloring material, a metal complex dye, a salt-forming dye, a dye which has dyed a dye to a resin, or the like. Among these, alcohol-soluble dyes such as salt-forming dyes which are easily dissolved in an organic solvent, oil-soluble dyes, and the like are preferable in terms of solubility and emulsion stability. Particularly suitable dyes are oil-soluble dyes. The lower limit blending amount of the dye is preferably 0_3% or more based on the total mass of the ink composition. If it is less than 3%, the coloring power is insufficient. Further, the blending amount of the upper limit is preferably 70% or less based on the mass of the total amount of the oily solution. If it exceeds 70%, the dissolution of the dye becomes difficult, and it is not suitable as an ink composition of a ballpoint pen. Particularly suitable is in the range of 1 to 3% based on the mass of the ink composition, and is in the range of 10 to 60% based on the mass of the oily solution. As the oil-based ink composition used in the salt-dyeing department, there is VALIFASTCOLAR (registered trademark, Orient Chemical Industries, Ltd.) VIII Spilon (love dyeing) Sipi) dye, Aizen Spilon SOT dyeing department (1 main volume trademark 12 201200569, Baotu Valley Chemical Industry Co., Ltd.). A dye used to dye dyes to resins, including keiko-Colot MPI-500 series, keiko-Colot MPI-500C series, keiko-Colot NKS-1000 series (registered trademark, Japanese fluorescent chemistry ( Stock system)). The coloring material in the oil phase can be used in combination with a small amount of pigment and dye as long as it can maintain the stability of the emulsion. In the case of using a pigment, the amount of the pigment is preferably 1% by weight or less based on the mass of the oily solution. If it exceeds 10%, there will be something wrong with the stability of the emulsion. In the oily phase, the pigment which can be used in combination with the dye may, for example, be an inorganic pigment such as carbon black or titanium oxide, an anthraquinone pigment, an azo pigment, a pyrrolopyrrolodione (Diketopyrrolopyrrole) pigment, or an anthraquinone pigment. Various organic pigments such as an anthraquinone pigment, a 1-isoindolone pigment, and an acridone pigment. In the oily solution for the weekly preparation of the ink composition of the present invention, a resin may be used to adjust the viscosity. The viscosity of the above oily solution is preferably 500 to 1,000, 00 〇 111 ? 3.3 at 25 ° C and a shear rate of 3.83 / sec in the absence of an emulsifier. If the viscosity is less than 5〇〇111?3.8, the water-breaking feeling will be generated when writing, and the performance of the oil-based ink obtained as the oil type in the water is not easy to exert. Moreover, the stability of the emulsion is not good. If it exceeds 1,000,000 mPa · s ', the pen feel becomes dignified, and it is not suitable as an ink composition of a ballpoint pen. The viscosity range of 3,000 to 500,000 mPa · s is particularly suitable at 25 ° C and a shear rate of 3.83 / sec. Specific examples of the resin which can be used in the ink composition of the present invention include ketone resin, continuous guanamine resin, maleic acid resin, olefinic resin, 萜13 201200569 olefin resin (terpene phen〇1 milk ratio) , ester glue, diterpene benzene resin, alkyd resin, expectant resin, turpentine, polyvinylpyrrolidone, polyvinyl butyral resin, polyvinyl alcohol, acrylic resin, melamine resin, cellulose resin, etc. For the natural and synthetic resins, one or two or more of these may be used. The amount of the dye and other additives in the oily solution is preferably from 3 to 70% based on the mass of the solid component of the total oily solution. When the solid content concentration is less than 3%, sufficient viscosity cannot be imparted. If it exceeds 70 ° /. 'The dissolution of the dye becomes difficult, and it is not suitable for the ink composition of the ballpoint pen. The solid content concentration is particularly preferably in the range of from 1% to 60%. The aqueous phase of the ink composition of the present invention is composed of a pigment dispersion. For example, the pigment dispersion system uses a pigment dispersion of ion-exchanged water or purified water. As the pigment, inorganic pigments such as carbon black and titanium oxide, anthraquinone pigments, azo pigments, pyrrolopyrroledione pigments, anthraquinone pigments, anthraquinone pigments, and 1-isoporphyrins can be used. Various organic pigments such as ketone pigments and acridone pigments. For example, 'CIPigment Black 1,7 'CIPigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 34, 35, 42, 53, 55, 65, 73, 74, 75, 81,83, 86, 93, 94, 95, 97, 98, 99, 100, 101, 104, 108, 109, 110, 114, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 167, 168, 173C, 174, 180, 185, etc.; CI Pigment Red (CI Pigment Red) 1 , 2, 3, 5, 7, 8, 9, 10, 12, 16, 17, 19, 22, 38, 41, 14 201200569 43, 48, 48 : 2, 48 : 3, 49, 50 : 1,52 , 53, 53 : 1,57, 57 : 1,58 : 2, 60, 63 : 1,63 : 2,64 : 1,86, 88, 90, 9, 112, 122, 123, 127, 146, 149 , 166, 168, 170, 175, 176, 177, 179, 180, 181, 184, 185, 189, 190, 192, 194, 198, 202, 206, 207, 209, 215, 216, 217, 220, 223 , 224, 226, 227, 228, 238, 240, 245, 254, 225, etc.; CI Pigment Blue 1, 2, 3, 15 : 1, 15 : 2, 15 : 3, 15 : 4 , 15 : 6, 16, 17, 22, 25, 60, 64, 66, etc.; CI Pigment Orannge (C_I. Pigment Orange) 5, 10, 13, 16, 36, 40, 43, 48, 49, 51, 55 , 59, 61, 71, etc.; CI Pigment Violet 1, 3, 5: 1, 16, 19, 23, 29, 30, 31, 33, 36, 37, 38, 40, 42, 50, etc.; CI Pigment Green (CI Pigment Green) 7, 10, 36, etc.; CI · Pigment Brown 23, 25, 26, etc. The color of the pigment dispersed in the aqueous phase may be the same as or different from the color of the dye dissolved in the oil phase. When a dye having the same color as the color of the pigment is used, the color of the ink can be made bright by the dye, and the color density can be improved. When a dye having a different color from the color of the pigment is used, a color change with a high degree of freedom can be obtained. The dispersing agent for obtaining the pigment dispersion can be used in various commercially available materials, and is not particularly limited, and is a polymer resin-based dispersing agent from the viewpoint of the phase stability and storage stability of the oil-in-water emulsion which is coexistent. It is better, and it is better to use it as an emulsifier to form an emulsion. For example, a styrene acrylic resin or a polyoxyethylene affixing agent can be used. A particularly suitable dispersant is a styrene acrylate resin which is a high molecular polymer.

15 S 201200569 在此所使用的顏料之量，係相料 τ相對於墨水組成物全質量 而為3-15%、較佳為5〜10%。顏料的息 , 叶的里若在3%以下，則作 為著色材之主成分上耐光性變差，# $ 走並且描線也欠缺濃度 感。顏料的量絲15%以上’ 的分韻定性 來看並不適宜。所使用的分散劑之量，’ 』<里，係相對於顏料分散 體之顏料總質量在20〜100%之範圍為佳。 ，例如，可舉藉由混 或使用球磨機、珠磨 超音波分散機、高壓 顏料朝水性相分散的分散方法中 合攪拌機均勻地混合各成分之方法、 機、親磨機、均質混合機、分散機、 均質機等分散機。 、又，水性相可含有基於防止低溫時墨水康結'防止筆 尖墨水乾燥為目的之添加劑，具體而言，可舉出乙一醇 —乙一醇、二乙二醇、丙二醇、聚乙二醇 吁1，二丁二醇、硫 代二乙二醇、丙三醇等的二醇類、乙二醇—甲 丁卷喊、二乙 二醇-甲基財賴等，可單獨或混合使用。添加劑的使 用量係以水性相之質量基準計為〇〜50%，較佳為〇〜3〇%。若 添加50%以上，則所得到的乳液之穩定性會有所不妥。 水性相係為求與前述油性溶液相混合以形成穩定的乳 液，而含有乳化劑。可與本發明之油性溶液的主溶劑相混 合並長期性地形成穩定的乳液之乳化劑，係分子骨架中具 有1個以上之芳香環的乳化劑。分子骨架中具有丨個以上之 芳香環的乳化劑’因為屬親油基之芳香環對油性相之染料 溶液親和性高’故可長期性地形成穩定的乳液。 本發明之墨水組成物中可使用作為芳香族系乳化劑 16 201200569 者要是具有1個以上芳香環之物，則並無特別限制。乳 化劑通常可藉由乙烯氧化物(EQ)加成莫耳數而改變性質。 牽連到油性溶液巾使_主_，乙職化物加成莫耳數 在40mol以上之物為佳。此乃因為藉由長鏈乙稀氧化物鍵， 可抑制粒子合一。 前述乙烯氧化物加成莫耳數在40mol以上的乳化劑，可 與對油性相之定向強的乙烯氧化物加成莫耳數在3〜i5m〇i 的乳化劑相組合使用。推測此乃因藉由組合使用對油性相 定向強之物與對水性相定向強之乳化劑，界面的微胞濃度 可提高，而增加乳液的穩定性。 關於HLB值(Hydrophile-Lipophile Balance;親水親油均 衡值），在非離子性界面活性劑方面較佳為至少使用1種 HLB值在15以上的乳化劑。這是由於即使乙烯氧化物加成 莫耳數偏夕，但右HLB值低，則乳化劑會被油性相側過多 没取。 作為具有乙烯氧化物40mol以上的乳化劑之物，可舉出 聚氧乙稀一本乙細化本謎、聚氧乙稀一苯乙稀化苯鱗、聚 氧乙稀戍基本謎專多環苯基型非離子界面活性劑；業已加 成乙烯氧化物鏈40mol以上之物；及其硫酸鹽等離子性界面 活性劑。關於乙烯氧化物加成莫耳數係以40mol以上且 200mol以下為佳。若屬業已加成200mol以上之乳化劑，則 黏度上升顯著，使用時會產生不適當的情形。 又，作為乙烯氧化物加成莫耳數3〜15之物，可舉聚氣 乙烯二苯乙烯化苯醚、聚氧乙烯一苯乙烯化苯醚、聚氧乙15 S 201200569 The amount of the pigment used herein is 3-15%, preferably 5 to 10%, based on the total mass of the ink composition. If the color of the pigment is less than 3% in the leaves, the light resistance is deteriorated as a main component of the coloring material, and the line is also lacking in concentration. It is not appropriate to determine the rhyme of the filament of the pigment above 15%. The amount of the dispersing agent to be used is preferably in the range of 20 to 100% based on the total mass of the pigment of the pigment dispersion. For example, a method, a machine, a grinder, a homomixer, and a dispersion in which a component is uniformly mixed by a mixer using a ball mill, a bead mill ultrasonic disperser, or a dispersion method of a high-pressure pigment in an aqueous phase dispersion may be used. Dispersing machine such as machine and homogenizer. Further, the aqueous phase may contain an additive for preventing the ink of the nib from drying at a low temperature, and specific examples thereof include ethyl alcohol-ethyl alcohol, ethylene glycol, propylene glycol, and polyethylene glycol. A glycol such as dibutyl diol, thiodiethylene glycol or glycerin, ethylene glycol-methyl butyl ketone or diethylene glycol-methyl ruthenium may be used singly or in combination. The amount of the additive to be used is 〇 50% by mass based on the mass of the aqueous phase, preferably 〇 3 to 3%. If 50% or more is added, the stability of the obtained emulsion may be inappropriate. The aqueous phase is mixed with the aforementioned oily solution to form a stable emulsion, and contains an emulsifier. It can be mixed with the main solvent of the oily solution of the present invention to form an emulsifier which forms a stable emulsion for a long period of time, and is an emulsifier having one or more aromatic rings in the molecular skeleton. An emulsifier having more than one aromatic ring in the molecular skeleton 'supplements because of the high affinity of the aromatic ring of the oleophilic group to the dye phase of the oily phase can form a stable emulsion for a long period of time. The ink composition of the present invention can be used as an aromatic emulsifier. 16 201200569 A material having one or more aromatic rings is not particularly limited. The emulsifier typically changes properties by adding a molar amount of ethylene oxide (EQ). It is preferred to add to the oily solution towel to make the _ main _, the yoke compound is added to the molar number of 40 mol or more. This is because the long-chain ethylene oxide bond can inhibit the uniformity of the particles. The emulsifier having an ethylene oxide addition molar number of 40 mol or more may be used in combination with an emulsifier having a molar orientation of an ethylene oxide addition molar number of 3 to i5 m〇i. It is presumed that this is because the combination of the oily phase-oriented material and the aqueous phase-oriented emulsifier can increase the cell concentration at the interface and increase the stability of the emulsion. Regarding the HLB value (Hydrophile-Lipophile Balance), it is preferred to use at least one emulsifier having a HLB value of 15 or more in terms of the nonionic surfactant. This is because even if the ethylene oxide is added to the molar number, the right HLB value is low, and the emulsifier is excessively taken from the oily phase side. Examples of the emulsifier having an ethylene oxide of 40 mol or more include polyoxyethylene, a refinement of the mystery, polyoxyethylene, styrene, styrene, and polyoxyethylene. a phenyl type nonionic surfactant; an additive having an ethylene oxide chain of 40 mol or more; and a sulfated plasma surfactant. The ethylene oxide addition molar number is preferably 40 mol or more and 200 mol or less. If an emulsifier of 200 mol or more is added, the viscosity rises remarkably, and an inappropriate situation may occur when used. Further, examples of the ethylene oxide addition molar number of 3 to 15 include polyoxyethylene distyrenated phenyl ether, polyoxyethylene monostyrene phenyl ether, and polyoxyethylene B.

S 17 201200569 烯戊基苯醚等多環苯基型非離子界面活性劑；業已加成乙 烯氧化物鏈3〜15mol之物；及其硫酸鹽等離子性界面活性 劑、聚氧乙烯烷基苯醚等之烷基苯酚型非離子性界面舌性 劑等。 ，’ ‘ 乳化劑係除了分子内具有芳香環的界面活性劑以外， 亦可追加添加具其他結構的任意乳化劑。例如，可舉聚氧 乙烯硬化蓖麻油、聚氧乙烯烷基(C10〜C18)酯等之直鏈烴型 非離子性界面活性劑、山梨醇酐衍生物等。乳化劑之量係 以油性溶液之質量基準計5〜150%為佳，1〇〜1〇〇%最佳。 除了顏料分散體 '乳化劑以外，水性相可含有水性圓 珠筆中通常使用的各種添加劑，例如防鏽劑、防腐劑' pH 調整劑、潤滑劑、保濕劑、樹脂、天然多醣類等增黏劑等。 本發明之水中油型水性圓珠筆用墨水組成物中，油性 相成分所佔的比例，係以質量基準計為卜川％，較佳為 3〜15%，更佳為5〜10%。油性相成分之比例一旦小於1〇/〇， 則無法獲得色濃度之提升、及在書寫性上滿足的性能，而 變得與一般水性圓珠筆無異。又，油性相成分之比例一旦 大於20%，則因為與顏料分散體的相互作用而可能導致乳 液不穩定化’再者，因油成分增加，而對描線乾燥性造成 不良影響。 乳液的平均粒子徑適宜在2〇〇nm以下，更適宜在15〇mn 以下。之所以令平均粒子徑在2〇〇nm以下，是為了抑制因粒 子的沉降或粒子彼此的衝突而導致合一。粒子徑的調整， 可採用後述乳化方法來控制，又，藉由使用高壓均質機等 18 201200569 乳化機的機械性剪斷力也可微細化。 本發明之水中油型乳液之乳化方法，可採用習知技術 中所知的各種乳化方法，例如相轉換乳化法(phase inversion emulsification)、D相乳化法(D-phase emulsification ;界面活 性劑乳化法）、PIT 乳化法（Phase Inversion Temperature emulsification ;相轉換溫度乳化法）、機械性乳化法。舉例 言之，在相轉換乳化法中’本發明之水中油型乳液可依據 以下步驟製造： a) 於有機溶劑中’將至少含有作為著色材之染料的油 性溶液成分加以授拌，使固形物成分溶解之步驟； b) 於水性成分添加乳化劑加以攪拌使之溶解之步驟； c) 將步驟a中所得之油性溶液一面攪拌並一面緩緩添 加步驟b +所得之水性成分以獲得水中油魏液之步驟； d) 面搜拌並進—步添加水性成分，經過相轉換而獲 得水中油型乳液之步驟。 調製3有顏料分散體之水性相的步驟係可採用習知 水性顏料墨水的方法。例如： a) 於攪拌機授拌顏料、分散劑、溶劑及pH調整劑3小 時之步驟； b) 於混砂機分散5小時之步驟； )X離〜刀離機除去上述顏料分散液的粗大粒子之 步驟； )稀釋上述顏料分散液，添加其他成分的步驟。 將如上述所δ周製之水中油型乳液、與含有顏料分散體S 17 201200569 Polycyclic phenyl type nonionic surfactants such as allyl phenyl ether; 3~15mol of ethylene oxide chain added; and its sulfate surfactant, polyoxyethylene alkyl phenyl ether Or an alkylphenol type nonionic interface lingual agent. The emulsifier is a surfactant which has an aromatic ring in the molecule, and may be added with any emulsifier having another structure. For example, a linear hydrocarbon type nonionic surfactant such as polyoxyethylene hardened castor oil or a polyoxyethylene alkyl (C10 to C18) ester, a sorbitan derivative or the like can be given. The amount of the emulsifier is preferably from 5 to 150% by mass based on the mass of the oily solution, and most preferably from 1 to 1%. In addition to the pigment dispersion 'emulsifier, the aqueous phase may contain various additives commonly used in water-based ballpoint pens, such as rust inhibitors, preservatives' pH adjusters, lubricants, humectants, resins, natural polysaccharides and other tackifiers. Wait. In the ink composition for a water-oil type water-based ballpoint pen of the present invention, the proportion of the oily phase component is, based on the mass basis, ib%, preferably 3 to 15%, more preferably 5 to 10%. When the ratio of the oily phase component is less than 1 〇/〇, the improvement in color density and the performance satisfactory in writing property cannot be obtained, and it becomes no different from a general water-based ballpoint pen. Further, when the ratio of the oil phase component is more than 20%, the emulsion may be destabilized due to the interaction with the pigment dispersion. Further, as the oil component increases, the dryness of the line is adversely affected. The average particle diameter of the emulsion is suitably 2 nm or less, more preferably 15 〇 mn or less. The reason why the average particle diameter is 2 〇〇 nm or less is to suppress the aggregation due to sedimentation of particles or collision of particles. The adjustment of the particle diameter can be controlled by the emulsification method described later, and by using a high-pressure homogenizer, etc. 18 201200569 The mechanical shearing force of the emulsifier can also be made fine. The emulsification method of the oil-in-water emulsion of the present invention may be carried out by various emulsification methods known in the prior art, such as phase inversion emulsification, D-phase emulsification, and surfactant emulsification. ), PIT emulsification (Phase Inversion Temperature emulsification), mechanical emulsification method. For example, in the phase inversion emulsification method, the oil-in-water emulsion of the present invention can be produced according to the following steps: a) in an organic solvent, 'mixing an oily solution component containing at least a dye as a coloring material to a solid matter a step of dissolving the component; b) a step of adding an emulsifier to the aqueous component and stirring to dissolve it; c) stirring the oily solution obtained in the step a while slowly adding the aqueous component obtained in the step b + to obtain the oil in the water The step of the liquid; d) the step of mixing and adding the step of adding the aqueous component, and converting the phase to obtain the oily emulsion in the water. The step of preparing the aqueous phase of the pigment dispersion is a conventional aqueous pigment ink. For example: a) the step of mixing the pigment, dispersant, solvent and pH adjuster in the mixer for 3 hours; b) the step of dispersing for 5 hours in the sand mixer; ) removing the coarse particles of the above pigment dispersion by removing the knife from the knife a step of: diluting the above pigment dispersion and adding other components. An oil-in-water emulsion prepared as described above and a pigment dispersion containing

S 19 201200569 之水性相加以攪拌混合。該攪拌混合係可採用以混合攪拌 機均勻地混合各成分之方法、或使用球磨機、珠磨機'輥 磨機、均質混合機、分散機、超音波分散機、高壓均質機 等分散機將各成分予以分散混合之方法。此時，可將油相 成分與水性相成分同時攪拌混合或分散混合皆可，又，將 各成分依序攪拌混合或分散混合也無妨。 再者，在製造水中油型乳液之際作為水性成分之物， 係可使用先前已調製之顏料分散體，不過因考量到以相轉 換乳化等進行相轉換之際，對顏料分散系造成不良影響， 故水中油型乳液製造步驟與顏料分散步驟宜分開進行。 本發明之水性圓珠筆用墨水組成物的黏性係以2 5 °C剪 斷速度380/秒之黏度在1〜l〇〇mPa · s為佳，更以5〜50mPa . s 為佳。若在lOOmPa · s以上，則因墨水黏性高，結果會使墨 水替換芯（refill)内之墨水追從性惡化，故不適宜。 實施例 以下，利用最具代表性的實施例，具體說明本發明之 較佳態樣與其優異效果。又，以下之「份」全部是指質量 份’「％」全部是指質量％。 針對實施例1〜18，如以下所示進行墨水組成物之調製。 首先，一面授拌表1所記載之油性溶液成分，一面於5〇。匚 〜60°C之溫度加溫，使該等成分完全溶解。表中的油性溶液 黏度係該溶液之值。另一方面，與此分開而另行將表2所記 載之乳化劑，於精製水一面搜拌一面使之溶解而製成乳化 劑水溶液。又，若是摻混對油性相定向強的乳化劑時，亦 20 201200569 可添加於該油性溶液中於常溫下攪拌。 21 201200569 1< o 寸 — m in m Ό CN 〇 «η 350000 實施例 17 (N un - l〇 mm Ό 18000 5 — — 一 CN 一 Ό p *〇 35000 省!2 鉍 CN 卜 ο rn 寸 rn Ο ο 10000 5 省2： 0.125 〇 o 〇 0.025 〇 s o VI P »〇 p u-j ο 30000 i 二 «η CN »〇 CN v> (N <N •η fN Ό (N (N Ό CN tn (Ν ο >n 30000 實施例 12 00 00 00 α\ 00 00 00 00 00 Ο JO 30000 實施例 11 m (N (Ν — 一 — Ό CN un 赛 40000 镩Ξ 一 Ο 00 d 00 o τί; 00 〇 νο ο 窆 120000 實施例 9 CN (N iTi Ο - - ON 〇 Ό Γ ΟΟ m 2500 實施例 8 卜 (N - 卜 Ο m CN <5 ο ο 寸 20000 實施例 7 - r-； ο ο ο 15000 實施例 6 m <N <N (N <N 寸 卜 vS 8000 實施例 5 ΓΟ <N CN (N (N 寸 卜 ro 8000 實施例 4 - 一 (N rj (N - 寸 »rj r^> 8000 實施例 3 »/Ί Ο — o •ΤΊ 〇 — u-> ο V) 〇 — l〇 对 v〇 CO 12000 實施例 2 (N in o 一 ^T) - VO CN 赛 40000 實施例 1 »Λ> (N - 一 一 «η d 一 一 一 — Ο 30000 油性溶液成分 VAL 丨 FASTV 丨 OLET 170UX1) fSpilon VIOLET CRH(^2) Spilon YWLLOW CGNH(^2) Oilblue613^1) 「Spilon RED (:^叫※〗） 「VALIFAST BLACK 3810(浓 1) VAUFAST RED 2320淡1) OilblackNO_5(《l) f松脂5叫糸3);酮樹脂 「YS波里斯特(示° U只夕一川丨以※々）；ii烯盼樹脂 「¥醇 苄二醇(benzyl glycol) 丙二醇一笨醚 二丙二醇二笨甲酸酯 二乙二醇二苯甲酸酯 「乙二醇一笨醚 笨二曱酸2-乙基己酯 |檸檬酸三丁基乙酸酯 三丙二醇一丁基醚 「坑基磺酸笨酯 Nikano丨LLL(※5};液狀二曱笨樹月旨 t4 ®- Ί 芳香族系程序用油(process oil) 油性溶液成分合計 油性溶液固形物成分濃度(％) 油性溶液黏度(mPa · s) 。ϋπ<·ί轶 T(lpnd)firif:们※。ntg<-5(lvoMtuHuv>IVHnsv>-¥^4杳？fta:寸※：ιιΠΓ<·5(ον5ι:3Η)友尨：ε※：l$tg<-4^JJJ-^-Msii:fN※：鉍CSSIIT^qt^^: 一※ 22 201200569The aqueous phase of S 19 201200569 is stirred and mixed. The stirring and mixing system may be a method in which the components are uniformly mixed by a mixing mixer, or a dispersing machine such as a ball mill, a bead mill, a roll mill, a homomixer, a disperser, an ultrasonic disperser, or a high-pressure homogenizer. Disperse and mix. In this case, the oil phase component and the aqueous phase component may be stirred, mixed or dispersed at the same time, and the components may be stirred or dispersed or mixed in sequence. Further, in the case of producing an oil-based emulsion in water, as the aqueous component, a previously prepared pigment dispersion can be used, but the pigment dispersion system is adversely affected by the phase transition by phase-conversion emulsification or the like. Therefore, the oil-in-water emulsion manufacturing step and the pigment dispersion step should be carried out separately. The viscosity of the ink composition for a water-based ballpoint pen of the present invention is preferably 1 to l 〇〇 mPa · s at a shear rate of 380 / sec at 25 ° C, more preferably 5 to 50 mPa · s. If it is at least 100 mPa·s or more, the ink is highly viscous, and as a result, the ink followability in the ink replacement core is deteriorated, which is not preferable. EXAMPLES Hereinafter, preferred embodiments of the present invention and their excellent effects will be specifically described using the most representative examples. In addition, the following "parts" all mean that the mass "%" means all the mass%. With respect to Examples 1 to 18, the preparation of the ink composition was carried out as follows. First, the oily solution components described in Table 1 were mixed and mixed at 5 Torr.加 Warm up to a temperature of ~60 ° C to completely dissolve the ingredients. The oily solution viscosity in the table is the value of the solution. On the other hand, separately from this, the emulsifier described in Table 2 was separately mixed with purified water to prepare an emulsifier aqueous solution. Further, in the case of blending an emulsifier having a strong orientation to the oil phase, 20 201200569 may be added to the oily solution and stirred at normal temperature. 21 201200569 1<o inch-m in m Ό CN 〇«η 350000 Example 17 (N un - l〇mm Ό 18000 5 — — one CN one Ό p * 〇 35000 province! 2 铋CN 卜 ο rn rn Ο ο 10000 5 Province 2: 0.125 〇o 〇0.025 〇so VI P »〇p uj ο 30000 i 二«η CN »〇CN v> (N <N •η fN Ό (N (N Ό CN tn (Ν ο >n 30000 Example 12 00 00 00 α\ 00 00 00 00 00 Ο JO 30000 Example 11 m (N (Ν - 一 - Ό CN un 赛40000 镩Ξ 一 00 00 00 o τί; 00 〇νο ο窆120000 Example 9 CN (N iTi Ο - - ON 〇Ό Γ ΟΟ m 2500 Example 8 卜 (N - Ο m m < 5 ο ο 00 00 00 00 00 00 00 6 m < N < N (N < N inch Bu vS 8000 Example 5 ΓΟ < N CN (N (N inch rob 8000) Example 4 - one (N rj (N - inch »rj r^> 8000 embodiment 3 »/Ί Ο - o • ΤΊ 〇 - u-> ο V) 〇 - l〇 vs v〇CO 12000 Example 2 (N In o a ^T) - VO CN 赛40000 Example 1 »Λ> (N - one-to-one «η d one-one - Ο 30000 oily solution composition VAL 丨FASTV 丨OLET 170UX1) fSpilon VIOLET CRH(^2) Spilon YWLLOW CGNH(^2) Oilblue613^1) "Spilon RED (:^叫※〗) "VALIFAST BLACK 3810 (concentrated 1) VAUFAST RED 2320 light 1) OilblackNO_5 ("l) f rosin 5 called 糸3); ketone resin "YS Boris (showing U U 夕一川一丨※々); ii olefins expectant resin "benzyl alcohol benzyl glycol (propylene glycol) propylene glycol monoether dipropylene glycol dimercapto diethylene glycol dibenzoic acid Ester "ethylene glycol monoether ether 2-ethylhexyl phthalate] tributyl citrate tripropylene glycol monobutyl ether "Pityl sulfonate ester Nikano 丨 LLL (※ 5}; liquid曱 曱 树 月 t t4 ® - 芳香族 aromatic process oil (oil) oily solution total oily solution solid content concentration (%) Solution viscosity (mPa · s). Ϋπ<·ί轶 T(lpnd)firif: **. Ntg<-5(lvoMtuHuv>IVHnsv>-¥^4杳?fta: inch ※: ιιΠΓ<·5(ον5ι:3Η) Friends: ε※:l$tg<-4^JJJ-^-Msii:fN※ :铋CSSIIT^qt^^: One ※ 22 201200569

n9_JAyuNos#^^T : Ξ※：'HlCDp3c£:dda.sZE3Jl5«(.sdEfEq!u4Ba3v : 6※ :0lsp3Ή!fnIJ.i¢砧<·4:l-<a3^^i«:8※：卜<N6寸3ns3ul>.uϊ¢¾«τq^-窠BY:r'※：00l-VIΛl¾¾l-JJ^^淑3·:9※ s 23 201200569 接著，將前述乳化劑水溶液一面攪拌並—面朝油性溶液 中緩緩添加，藉此使之從W/O相轉換至0/W相，而獲得水中油 型之乳液。之後，關於實施例丨〜4、6〜9、η〜18、比較例4係 採用市售之高壓均質機，進行乳化處理直至到達預定平均粒 子徑為止。又，不針對實施例5、10進行高壓均質機處理。 平均粒子徑之測定係利用粒子徑測定器N4pius(庫爾 特(COULTER)公司製）進行測定。測定時，係以水稀釋直至 樣本試料到達N4Plus之推薦濃度為止，且係以25。(：之溫度 條件測定。又’本申請案之說明書中所使用的平均粒子徑 之用語’係意指中位數徑。 依據上述步驟，而另行製成顏料濃度20%之顏料分散體。 對業已製成之顏料分散體，進行d)步驟之稀釋及其他 成分添加’以使最終的墨水成分量成為表2所示。又，此時， 前述乳化劑水溶液中所使用的各成分之量，係減量調整。 以分散機將上述水中油型乳液與顏料分散體進行混合 攪拌’並針對實施例10、11、16及比較例4，係於最後擭拌 使增黏劑成分溶解，而獲得本發明之墨水組成物。 在墨水的黏度測定方面，係利用德國哈凱公司（Thermo Haake GmbH)製流變儀、型號：RheoStress600。圓錐係採 用直徑20mm、傾斜角1度之物。測定條件係於25°C剪斷速 度380/秒之條件下，測定3〇秒鐘，以業已穩定之數值為黏度。 將實施例1〜18中所生成的各組成物組入三菱錯筆（股) 製UMR-07替換芯之轴，進行以下評價。 準備表3所記載之墨水組成物作為比較例1〜4。而且， 24 201200569 比較例4係本案申請人先前 〜已申請之申請案日本特願 2008-145150號說明書中的警始/ 貝死•例1之墨水組成物。比較例1 中係將墨水充填於三菱鉛筆制 掌（月又）製SA-07N替換芯，比較例2 及比較例4中係將墨水充填於= —曼鉛筆（股）製UMR-07替換 芯，比較例3中係將墨水充埴妒^ ^ 凡具於二窆鉛筆（股）製UB157軸， 將墨水分別按此充填，以之進行評價。 表3 比較例墨水組成 比較例1 比較例2 比較例3 比較例4 VALIFAST BLACK381 (^※ 1) VALlFASTVIOLETli0i(※万 … •讎··——····_·•讎·一 10 10 〇 Spilon VIOLET •一·一一垂•冊•一一喔_ 7 5 0 OilblackN0.5^1) — 鲁»一垂垂__ 0 Spilon YELLOW 5 云乙^°比咯啶酮 0.5 松脂SK^4);酮樹脂 7 0 nikanol HP120(^3);二甲苯樹脂 0苄醇 苯乙二醇 ~"_2〇"… ~~_36.5 ~~ 2 …’-厂 〇 二丙二醇二苯甲酸酯 15 油酸 3 ΝΥΜΕΕΝ ；ΡΟΕ 月桂ϋ 1 碳黑 7 7 笨乙烯丙烯酸樹脂 2 2 磷酸酯 0.5 0.5 三乙醇胺 0.5 0.5 苯并*** 0.3 0.3 W 丙三醇 10 乙二醇 20 丙二醇 15 二乙二醇 10 Ε ΡΟΕ(ΙΟ)二苯乙烯化苯醚(HLB 14) 0.5 E POE(80)二苯乙烯化笨謎(Ηίέ 19) 9 W精製水 64.2 69.7 50.1 W三仙膠 0.5 0.4 計 100 100 100 100 ※l :東方化學工業(股)製；※2 :保土谷化學公司製 ^4 :赫斯(HiilsAG)公司製；※5 :曰油公司製。 ※^ :福德(Fudow)工業公司製 注)比較例4中，Ο :油性成分’ W :水性相成分，E :作為乳化劑，準照實施例1製成。n9_JAyuNos#^^T : Ξ※:'HlCDp3c£:dda.sZE3Jl5«(.sdEfEq!u4Ba3v : 6※ :0lsp3Ή!fnIJ.i ¢ anvil<·4:l-<a3^^i«:8※ :卜<N6 inch 3ns3ul>.uϊ¢3⁄4«τq^-窠BY:r'※:00l-VIΛl3⁄43⁄4l-JJ^^淑3·:9※ s 23 201200569 Next, the aqueous emulsifier solution is stirred while stirring - Adding slowly to the oily solution, thereby converting it from the W/O phase to the 0/W phase, and obtaining an oil-type emulsion in water. Thereafter, regarding the examples 丨~4, 6~9, η~18, In Comparative Example 4, a commercially available high-pressure homogenizer was used to carry out emulsification treatment until reaching a predetermined average particle diameter. Further, high-pressure homogenizer treatment was not performed for Examples 5 and 10. The measurement of the average particle diameter was performed by using a particle diameter measuring device N4pius. (Measured by COULTER Co., Ltd.). When measuring, it is diluted with water until the sample sample reaches the recommended concentration of N4Plus, and is determined by the temperature condition of 25. (In the specification of this application) The term "average particle diameter" used means the median diameter. According to the above procedure, a pigment dispersion having a pigment concentration of 20% is separately prepared. For the pigment dispersion which has been prepared, the dilution of the step d) and the addition of other components are carried out so that the final amount of the ink component is as shown in Table 2. Further, at this time, the amount of each component used in the aqueous emulsifier solution is , the amount of adjustment is adjusted. The above oil-in-water emulsion and the pigment dispersion are mixed and stirred by a disperser, and for the examples 10, 11, 16 and the comparative example 4, the tackifier component is dissolved in the final mixing to obtain In the ink composition of the present invention, a rheometer manufactured by Thermo Haake GmbH, model: RheoStress 600 is used for measuring the viscosity of the ink, and the cone is made of a material having a diameter of 20 mm and a tilt angle of 1 degree. The measurement was carried out for 3 sec seconds at a shear rate of 380 / sec at 25 ° C, and the viscosity was established as a stable value. The compositions obtained in Examples 1 to 18 were incorporated into the Mitsubishi stylus (stock) system. UMR-07 replaced the core of the core, and the following evaluation was performed. The ink compositions described in Table 3 were prepared as Comparative Examples 1 to 4. Moreover, 24 201200569 Comparative Example 4 is the applicant's previous application to the applicant. In the instruction manual of 2008-145150, the ink composition of Example 1 was used. In Comparative Example 1, the ink was filled in a SA-07N replacement core made by Mitsubishi Pencil Palm (Month), Comparative Example 2 and Comparative Example In the middle of the system, the ink is filled in the UMR-07 replacement core made of =-man pencil (share), and the ink is filled in the comparison example 3. ^^ The UB157 axis is made of the second pencil (share), and the ink is pressed separately. This filling is used for evaluation. Table 3 Comparative Example Ink Composition Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 VALIFAST BLACK381 (^※ 1) VALlFASTVIOLETli0i (※ Wan... • 雠····························· VIOLET • 一·一一垂•册•一一喔_ 7 5 0 OilblackN0.5^1) — Lu » a drooping __ 0 Spilon YELLOW 5 Yun B ^ ° pyrrolidone 0.5 rosin SK ^ 4); Ketone resin 7 0 nikanol HP120 (^3); xylene resin 0 benzyl alcohol phenyl glycol ~ "_2〇"... ~~_36.5 ~~ 2 ...'-Factory dipropylene glycol dibenzoate 15 Oleic acid 3 ΝΥΜΕΕΝ ; ΡΟΕ laurel ϋ 1 carbon black 7 7 stupid ethylene acrylic resin 2 2 phosphate 0.5 0.5 triethanolamine 0.5 0.5 benzotriazole 0.3 0.3 W glycerol 10 ethylene glycol 20 propylene glycol 15 diethylene glycol 10 Ε ΡΟΕ(ΙΟ) distyryl phenyl ether (HLB 14) 0.5 E POE (80) distyrylation (Ηίέ 19) 9 W refined water 64.2 69.7 50.1 W Sanxianjiao 0.5 0.4 Meter 100 100 100 100 ※l : Oriental Chemical Industry Co., Ltd.; ※2: Batu Tugu Chemical Co., Ltd. ^4: Hess ( HiilsAG) company system; ※5: made by the company. *^: manufactured by Fudow Industrial Co., Ltd. Note) In Comparative Example 4, Ο: oily component 'W: aqueous phase component, E: emulsified as an emulsifier, which was prepared in the same manner as in Example 1.

S 25 201200569 <評價> (a) 耐沉降性試驗 將業已使筆尖部朝向離心方向的替換芯在迴轉半徑 20cm、迴轉數2000rpm(約900G)之條件下進行離心5小時， 之後於書寫用紙上書寫直徑約2cm之圓，與離心處理前之描 線濃度進行比較。 ◎:與初始濃度無差異。 〇：描線稍濃但書寫上沒有問題。 △:可清楚識別出描線濃，但仍可書寫。 ♦:描線濃且筆跡之模糊很顯眼，不堪使用。 X :無法書寫。 (b) 筆感輕盈流利試驗 於書寫用紙書畫5圈，如以下所示判定筆感之輕重。 ◎:非常輕盈流利。 〇：輕盈流利。 △:普通。 ♦:沉重遲滯。 X :不堪使用。 (c) 斷水感試驗 如以下所示，對(a)中記載之筆感輕盈流利試驗時的書 寫斷水感進行判定。 ◎:完全不以為意。 〇：有些許感覺但沒有問題。 △:稍微令人在意。 26 201200569 ♦:頗為在意。 X :在意。 (d) 对水性試驗 將業已書寫於書寫用紙之描線以水濕潤，觀察1分鐘後 的狀態。 ◎:描線完全沒有變化。 〇：描線稍可觀察到染潰但不構成問題。 △:描線上染潰很醒目但仍可判別。 X:判別困難。 (e) 对光性試驗 將業已書寫於書寫用紙之描線暴露於曰光下12小時， 判定褪色程度。 ◎:完全未褪色。 〇：有若干褪色但仍可清楚辨識。 △:可確認殘存描線。 X:完全無法辨識。 (f) 描線濃度試驗 將業已書寫於書寫用紙之描線與比較例之水性墨水、 凝膠墨水之描線以目測進行比較。 ◎:較之比較樣本濃。 〇：與比較樣本同等。 △:較之比較樣本稍嫌拙劣。 X:較之比較樣本拙劣。 (g) 描線乾燥性試驗S 25 201200569 <Evaluation> (a) The sedimentation resistance test was carried out by centrifuging the replacement core having the tip end portion in the centrifugal direction at a radius of rotation of 20 cm and a number of revolutions of 2000 rpm (about 900 G) for 5 hours, and then on the writing paper. A circle having a diameter of about 2 cm was written on it and compared with the concentration of the line before centrifugation. ◎: There is no difference from the initial concentration. 〇: The line is slightly thick but there is no problem in writing. △: The line is thickly recognized, but it can still be written. ♦: The line is thick and the blur of the handwriting is conspicuous and unbearable. X: Can't write. (b) Light and fluent test of pen feel 5 strokes of writing and calligraphy, as shown below to determine the weight of the pen. ◎: Very light and fluent. 〇: Light and fluent. △: Normal. ♦: Heavy delay. X: Unbearable use. (c) Water sensation test As shown below, the water sensation in the light fluency test described in (a) is judged. ◎: I don't care at all. Hey: I feel a little but no problem. △: Slightly noticeable. 26 201200569 ♦: I am quite concerned. X: Care. (d) For the water-based test, the line which has been written on the writing paper was wet with water and observed after 1 minute. ◎: The line is completely unchanged. 〇: The line is slightly observable and does not pose a problem. △: The dyeing on the line is very conspicuous but still discriminable. X: It is difficult to judge. (e) For the light test, the line drawn on the writing paper was exposed to twilight for 12 hours to determine the degree of fading. ◎: Completely fading. 〇: There are some fading but still clearly identifiable. △: The remaining trace can be confirmed. X: Completely unrecognizable. (f) Line drawing density test The line drawn on the writing paper and the line drawing of the aqueous ink and the gel ink of the comparative example were visually compared. ◎: Thicker than the comparison sample. 〇: Same as the comparison sample. △: It is a bit worse than the comparison sample. X: Poor compared to the comparison sample. (g) Line drying test

S 27 201200569 將業已書寫於書寫用紙之描線，於10秒後以塑膠袋片 擦過，確認描線的延伸程度與污損。 ◎:完全未延伸，描線也無污損。 〇_邊乎/又有延伸，描線也無污損。 △:描線稍有延伸。 X:描線有污損。 ⑴保存穩定性試驗 將筆體於50°C之條件下放置3個月，確認書寫性。 ◎:與初始毫無變化。 〇：與初始相較有些微變化，但書寫上不構成問題。 △:可觀察到描線之劣化，但仍可書寫。 ♦:描線顯著劣化。 X :無法書寫。 上述試驗之結果顯示於表4〜表6。由該等結果可得知， 本發明之墨水組成物較之比較例墨水（油性墨水、凝膠墨 水、水性墨水、本案申請人之先前發明）’展現出優越的結果。 評價 1 實施 2 —實施Θ 3 —實施S 4 實施例 5 實施例 6 墨水黏度(mPa · s) 30 15 10 90 90 90 一德····—一一·· 乳化物：平均粒子徑(nm) 80 100 120 110 250 耐沉降性 __————- ◎ _—·一— ◎ © ◎ •參—》···_· Δ 〇 •響_—辦~___——垂 筆感輕盈流利 ------- ◎ «··一一— ◎ ◎ @ @ ------------—---- 斷水感 ____——- ◎ ◎ ·—◎ δ @ © ------------------------- 耐水性 _______ ◎ ◎ ""δ δ © ----------------------- 耐光性 ◎ ◎ ◎ © © 描線濃度 ----- ◎ —— ◎ "© 5 © _ @ 描線乾燥性 ------— ◎ ◎ —◎ ◎ © @ — 保存穩定性 —— ◎ ^ _ ————— ◎ ·—◎ 5 δ @ 30 140 "© ©" —δ: Δ 35 160 〇 ◎ ◎ ◎ ◎ ————· ◎ ◎ Δ 10 ----- 180 〇 ◎一 ©_ ◎ Δ 28 201200569 表5 評價 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 10 11 12 13 14 15 16 17 18 墨水黏度(mPa _ s) 45 50 300 900 5 25 8 15 700 乳化物：平均粒子徑(nm) 220 170 80 80 80 130 100 110 100 耐沉降性 Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 筆感輕盈流利 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 斷水感 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 耐水性 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 耐光性 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 描線濃度 ◎ ◎ ◎ ◎ Δ 〇 〇 ◎ 〇 描線乾燥性 ◎ ◎ 〇 Δ ◎ ◎ ◎ ◎ Δ 保存穩定性 Δ 〇 〇 Δ ◎ Δ Δ 〇 ◎ 表6 評價 比較例1 比較例2 比較例3 比較例4 墨水黏度(mPa · s) 6000 50 5 1200 乳化物：平均粒子徑(nm) — — — 100 耐沉降性 — — — ◎ 筆感之輕盈流利 Δ 〇 ◎ ◎ 斷水感 ◎ ♦ ♦ ◎ 耐水性 〇 ◎ ◎ 〇 耐光性 ♦ ◎ ◎ ♦ 描線濃度 ♦ 〇 〇 〇 描線乾燥性 〇 Δ 〇 Δ 保存穩定性 ◎ ◎ ◎ ◎ I：圖式簡單說明3 (無） 【主要元件符號說明】 (無） 29S 27 201200569 The line that has been written on writing paper is rubbed with a plastic bag after 10 seconds to confirm the extension of the line and the stain. ◎: It is not stretched at all, and the line is also not stained. 〇 _ _ / / / extension, the line is also not defaced. △: The drawing line is slightly extended. X: The line is stained. (1) Storage stability test The pen body was allowed to stand at 50 ° C for 3 months to confirm the writing property. ◎: No change from the initial. 〇: There are some slight changes from the initial one, but writing does not pose a problem. △: Deterioration of the line was observed, but writing was still possible. ♦: The trace is significantly degraded. X: Can't write. The results of the above tests are shown in Tables 4 to 6. From these results, it is understood that the ink composition of the present invention exhibits superior results as compared with the comparative ink (oily ink, gel ink, aqueous ink, and the prior invention of the applicant). Evaluation 1 Example 2 - Implementation Θ 3 - Implementation S 4 Example 5 Example 6 Ink Viscosity (mPa · s) 30 15 10 90 90 90 One De································ 80 100 120 110 250 Resistance to settling __————- ◎ _—·一— ◎ © ◎ • 参—》····· Δ 〇•响__办~___——Light and fluent ------- ◎ «··一一— ◎ ◎ @ @ ------------—---- Water Sense ____——- ◎ ◎ ·——◎ δ @ © ------------------------- Water resistance _______ ◎ ◎ ""δ δ © ----------- ------------ Lightfastness ◎ ◎ ◎ © © Trace Concentration----- ◎ —— ◎ "© 5 © _ @ 线线干燥性———— ◎ ◎ — ◎ ◎ © @ — Storage stability ◎ ^ _ ————— ◎ ·——◎ 5 δ @ 30 140 "© ©" —δ: Δ 35 160 〇◎ ◎ ◎ ◎ ————· ◎ ◎ Δ 10 ----- 180 〇 ◎ _ _ _ _ _ 28 201200569 Table 5 Evaluation Example Examples Embodiments Examples Embodiments Examples Embodiments Example 10 11 12 13 14 15 16 17 18 Ink viscosity (mPa _ s) 45 50 300 900 5 25 8 15 700 Emulsion: Average particle diameter (nm) 220 170 80 80 80 130 100 110 100 Sedimentation resistance Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 line concentration ◎ ◎ ◎ ◎ Δ 〇〇 ◎ 〇 线 干燥 ◎ ◎ 〇 ◎ ◎ ◎ ◎ Δ Storage stability Δ 〇〇 Δ ◎ Δ Δ 〇 ◎ Table 6 Evaluation Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Ink viscosity (mPa · s) 6000 50 5 1200 Emulsifier: Average particle diameter (nm) — — — 100 Resistance to settling — — — ◎ Light and fluent Δ 〇 ◎ ◎ Water resistance ◎ ♦ ♦ ◎ Water resistance 〇 ◎ ◎ 〇 Light fastness ♦ ◎ ◎ ♦ Trace line concentration ♦ Dry line drying 〇 Δ 〇 Δ Storage stability ◎ ◎ ◎ ◎ I: Simple description of the figure 3 (none) [Explanation of main component symbols] (None) 29

Claims (1)

201200569 七、申請專利範圍： 1. 一種水性圓珠筆用墨水組成物，係對於顏料分散體所構 成之水性相，以水中油型乳液之狀態含有油性相，且該 油性相含有業已使染料溶解於有機溶劑中之油性溶液。 2. 如申請專利範圍第1項之水性圓珠筆用墨水組成物，其 中前述油性溶液之全溶劑中，分子骨架中具有一個以上 芳香環的溶劑係以質量基準計佔50%以上，且前述墨水 組成物含有分子骨架中具有一個以上芳香環的乳化劑。 3. 如申請專利範圍第2項之水性圓珠筆用墨水組成物，其 中前述乳化劑至少含有乙烯氧化物加成莫耳數為40以 上的芳香族系乳化劑。 4. 如申請專利範圍第1〜3項中任一項之水性圓珠筆用墨水 組成物，其中前述油性溶液之溶劑的沸點在200°C以上。 5. 如申請專利範圍第1〜4項中任一項之水性圓珠筆用墨水 組成物，其於25°C下對水的溶解度以質量基準計係1% 以下，且分子骨架中具有一個以上芳香環的溶劑在前述 油性溶液之全溶劑中以質量基準計係佔5 0%以上。 6. 如申請專利範圍第1〜5項中任一項之水性圓珠筆用墨水 組成物，其中前述水中油型乳液之油滴的平均粒徑為 200nm以下。 7. 如申請專利範圍第1〜6項中任一項之水性圓珠筆用墨水 組成物，其中該墨水組成物中所佔的油性相成分之比例 以質量基準計係1〜20%。 8. 如申請專利範圍第1〜7項中任一項之水性圓珠筆用墨水 組成物，其中前述顏料分散體中所含的分散劑為苯乙烯 丙烯酸樹脂。 30 201200569 四、指定代表圖： (一) 本案指定代表圖為：第（ ）圖。（無) (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：201200569 VII. Patent application scope: 1. A water-based ball-point pen ink composition containing an oily phase in the form of an oil-based emulsion for an aqueous phase composed of a pigment dispersion, and the oily phase contains the dye dissolved in the organic phase. An oily solution in a solvent. 2. The ink composition for a water-based ballpoint pen according to the first aspect of the invention, wherein, in the total solvent of the oily solution, a solvent having one or more aromatic rings in the molecular skeleton accounts for 50% or more by mass, and the ink composition is as described above. The substance contains an emulsifier having more than one aromatic ring in the molecular skeleton. 3. The ink composition for a water-based ballpoint pen according to the second aspect of the invention, wherein the emulsifier contains at least an aromatic emulsifier having an ethylene oxide addition molar number of 40 or more. The ink composition for a water-based ballpoint pen according to any one of claims 1 to 3, wherein the solvent of the oily solution has a boiling point of 200 ° C or higher. 5. The ink composition for a water-based ballpoint pen according to any one of claims 1 to 4, which has a solubility in water at 25 ° C of 1% or less on a mass basis and one or more fragrances in a molecular skeleton. The solvent of the ring accounts for more than 50% by mass based on the total solvent of the above oily solution. 6. The ink composition for a water-based ballpoint pen according to any one of claims 1 to 5, wherein the oil droplets of the oil-in-water emulsion have an average particle diameter of 200 nm or less. 7. The ink composition for a water-based ballpoint pen according to any one of claims 1 to 6, wherein the ratio of the oily phase component in the ink composition is 1 to 20% by mass. The ink composition for a water-based ballpoint pen according to any one of claims 1 to 7, wherein the dispersing agent contained in the pigment dispersion is a styrene acrylic resin. 30 201200569 IV. Designation of representative drawings: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: